High temperature bulk metathesis polymerization
A method of carrying out a metathesis reaction includes the combination of at least one alkene or non conjugated diene with a Ruthenium-based catalyst with an cyclic(alkyl)(amino)carbene ligand to form a reaction mixture, heating the reaction mixture to a temperature of 100° C. or greater in the absence of a solvent in bulk conditions, and mechanically stirring the reaction mixture. The reaction can be an ADMET, ROMP, a metathesis ring-closure or an olefin exchange reaction.
1. A method for producing a polymer via metathesis polymerization, the method comprising:
forming a polymerization mixture, the polymerization mixture comprising a Ruthenium-based catalyst comprising a cyclic (alkyl) (amino) carbene ligand, having the structure:
heating the polymerization mixture to a temperature greater than the melting point of the polymer in bulk conditions to form a molten polymerization mixture; and
performing intensive mixing on the molten polymerization mixture to produce the polymer,
wherein the polymer has a weight average molecular weight of at least about 10,000 Da within about 3 hours, and
wherein the melting point of the polymer is 100° C. or greater.
2. The method according to claim 1 , wherein the polymerization mixture further comprises one or more selected from
at least one cyclic monomer comprising an alkene,
at least one linear monomer comprising an α,ω-dieneyl-monomer,
and combinations thereof.
3. The method according to claim 2 , wherein the at least one cyclic monomer or the at least one linear monomer comprises a functional group selected from alkyl, aryl, alkylaryl, ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester, and amides.
4. The method according to claim 1 , wherein the metathesis polymerization is a metathesis ring-closure, and
wherein the polymerization mixture further comprises at least one acyclic non-conjugated diene.
5. The method of metathesis ring-closure according to claim 4 , wherein the at least one acyclic non-conjugated diene comprises a functional group selected from alkyl, aryl, alkylaryl, ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester, and amides.
6. The method according to claim 1 , wherein the metathesis polymerization is a metathesis olefin exchange, and
wherein the polymerization mixture further comprises at least one alkene.
7. The method of metathesis olefin exchange according to claim 6 , wherein the at least one alkene comprises a functional group selected from alkyl, aryl, alkylaryl, ketone, aldehyde, ether, ester, carboxylic acid, alkylsilyl, arylsilyl, alkylarylsilyl, amine, epoxy, sulfone, sulfonic acid ester, and amides.
8. The method according to claim 1 , wherein a degree of polymerization of from about 10 to about 100 is achieved in from about 3 to about 24 hours.
9. The method of metathesis polymerization according to claim 1 , wherein the temperature is 120° C. or greater.
10. The method of metathesis polymerization according to claim 1 , wherein the polymerization mixture further comprises a quinone.
11. The method of metathesis polymerization according to claim 10 , wherein the quinone is benzoquinone.